US20200062602A1 - Method for producing oligosilane - Google Patents

Method for producing oligosilane Download PDF

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Publication number
US20200062602A1
US20200062602A1 US16/335,990 US201716335990A US2020062602A1 US 20200062602 A1 US20200062602 A1 US 20200062602A1 US 201716335990 A US201716335990 A US 201716335990A US 2020062602 A1 US2020062602 A1 US 2020062602A1
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group
oligosilane
hydrosilane
transition elements
catalyst layer
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Kiyoshi Nomura
Hiroshi Uchida
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Resonac Holdings Corp
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Showa Denko KK
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Definitions

  • the present invention relates to a method for producing an oligosilane.
  • Oligosilanes such as hexahydrodisilane (Si 2 H 6 , hereinafter may be abbreviated as “disilane”) and octahydrotrisilane (Si 3 H 8 , hereinafter may be abbreviated as “trisilane”) are highly reactive as compared with tetrahydrosilane (SiH 4 , hereinafter may be abbreviated as “monosilane”) and very useful compounds as, for example, precursors for the formation of amorphous silicon and silicon films.
  • Non-Patent Document 1 the acid decomposition of magnesium silicide
  • Non-Patent Document 2 the reduction of hexachlorodisilane
  • Patent Document 1 electric discharge in tetrahydrosilane
  • Patent Documents 2 to 3 the thermal decomposition of silane
  • Patent Documents 4 to 10 the dehydrogenative coupling of hydrosilanes such as tetrahydrosilane using a catalyst
  • the oligosilane production method using the dehydrogenative coupling of a hydrosilane is an industrially excellent method with which an oligosilane can be produced at a relatively low cost using an inexpensive and readily available raw material, there has been room for improvement with this method with regard to the conversion of the reaction and the selectivity for a target oligosilane.
  • An object of the present invention is to provide an oligosilane production method with which a target oligosilane can be more efficiently produced.
  • the present inventors found out that in the dehydrogenative coupling reaction of a hydrosilane in which an oligosilane is produced from the hydrosilane, the oligosilane can be more efficiently produced by controlling the reaction step to satisfy specific conditions.
  • the present invention was achieved based on this finding.
  • the present invention is as follows.
  • a method for producing an oligosilane comprising a reaction step of introducing a fluid containing a hydrosilane into a continuous reactor provided with a catalyst layer inside to produce an oligosilane from the hydrosilane and discharging a fluid containing the oligosilane from the reactor, wherein
  • oligosilane production is carried out more efficiently.
  • FIG. 1 is a cross sectional view (schematic diagram) of a continuous reactor that can be used in the oligosilane production method that is one aspect of the present invention.
  • FIG. 2(A) is a cross sectional view of another continuous reactor that can be used in the oligosilane production method that is one aspect of the present invention
  • FIG. 2(B) is a schematic diagram showing temperature profiles.
  • FIG. 3(A) is a cross sectional view of still another continuous reactor that can be used in the oligosilane production method that is one aspect of the present invention
  • FIG. 3(B) is a schematic diagram showing temperature profiles.
  • FIG. 4(A) is a cross sectional view of yet another continuous reactor that can be used in the oligosilane production method that is one aspect of the present invention
  • FIG. 4(B) is a schematic diagram showing temperature profiles.
  • FIG. 5(A) is a cross sectional view of still another continuous reactor that can be used in the oligosilane production method that is one aspect of the present invention
  • FIG. 5(B) is a schematic diagram showing temperature profiles.
  • FIG. 6 is a schematic diagram of the reaction apparatus that was used in the Examples and Comparative Examples of the present invention.
  • the oligosilane production method that is one aspect of the present invention (hereinafter may be abbreviated as “production method of the present invention”) includes a reaction step of introducing a fluid containing a hydrosilane into a continuous reactor provided with a catalyst layer inside to produce an oligosilane from the hydrosilane and discharging a fluid containing the oligosilane from the reactor (hereinafter may be abbreviated as “reaction step”) and is characterized in that the reaction step satisfies all of the following conditions (i) to (iii):
  • a temperature of the hydrosilane-containing fluid at an inlet of the catalyst layer is higher than a temperature of the oligosilane-containing fluid at an outlet of the catalyst layer;
  • the temperature of the hydrosilane-containing fluid at the inlet of the catalyst layer is from 200 to 400° C.; and
  • the temperature of the oligosilane-containing fluid at the outlet of the catalyst layer is from 50 to 300° C.
  • the present inventors found out that, in the dehydrogenative coupling reaction of a hydrosilane in which an oligosilane is produced from the hydrosilane, the oligosilane can be more efficiently produced by controlling the reaction to satisfy all of the above-described conditions (i) to (iii).
  • Hydrosilane herein refers to a silane compound having at least one silicon-hydrogen (Si—H) bond.
  • Oletilane herein refers to a silane oligomer provided by the coupling of a plurality of (2 to 5) individual (mono)silane molecules.
  • Dehydrogenative coupling of a hydrosilane herein refers to a reaction in which the silicon-silicon (Si—Si) bond is formed by hydrosilane-to-hydrosilane coupling with the elimination of a hydrogen molecule (H 2 ), as represented by the following reaction formula.
  • the reaction step in the production method of the present invention is a step of producing an oligosilane from a hydrosilane in a continuous reactor provided with a catalyst layer inside, and this step may be carried out for example using a reactor shown in FIG. 1 .
  • a reactor 101 which is connected to an introduction pipe 102 and a delivery pipe 103 , is a continuous reactor capable of simultaneously performing introduction of a hydrosilane as a raw material and discharge of an oligosilane as a product.
  • a catalyst layer 106 is provided in a manner to be in contact with a fluid so that a fluid having passed through the catalyst layer 106 can be discharged.
  • the conditions (i) to (iii) above relate to “temperature of the hydrosilane-containing fluid at an inlet of the catalyst layer” and “temperature of the oligosilane-containing fluid at an outlet of the catalyst layer”, and “temperature of the hydrosilane-containing fluid at an inlet of the catalyst layer” corresponds to the temperature of a hydrosilane-containing fluid 104 immediately before coming into contact with the catalyst layer 106 , and “temperature of the oligosilane-containing fluid at an outlet of the catalyst layer” corresponds to the temperature of an oligosilane-containing fluid 105 immediately after being discharged from the catalyst layer 106 .
  • silylene is produced as follows: monosilane yields silylene and hydrogen when monosilane (tetrahydrosilane) is used as a raw material, or disilane (hexahydrodisilane) yields silylene and silane (tetrahydrosilane) when disilane (hexahydrodisilane) is used as a raw material, and the produced silylene reacts with silanes and grows (silylene reacts with monosilane (tetrahydrosilane) to produce disilane (hexahydrodisilane) when monosilane (tetrahydrosilane) is used as a raw material, or silylene reacts with dis
  • a concentration gradient occurs where the concentration of the raw material, tetrahydrosilane is high in the vicinity of the inlet of the catalyst layer and low in the vicinity of the outlet of the catalyst layer, whereas the concentration of the product, hexahydrodisilane is low in the vicinity of the inlet of the catalyst layer (the inlet concentration of disilane is zero when the product is not recycled in the production of disilane using monosilane as a raw material) and high in the vicinity of the outlet of the catalyst layer.
  • oligosilanes such as hexahydrodisilane are highly reactive as compared with tetrahydrosilane, by performing control so as to satisfy all of the conditions (i) to (iii) above, that is, by performing control so that the temperature is high in the vicinity of the inlet of the catalyst layer where the concentration of tetrahydrosilane is high while the temperature is low in the vicinity of the outlet of the catalyst layer where accumulated concentrations of hexahydrodisilane and higher oligosilanes are high, even though the reactivity of tetrahydrosilane is also decreased, side reactions due to further dehydrogenative reactions (via silylene) of more highly reactive oligosilanes such as hexahydrodisilane are suppressed, whereby a target oligosilane can be more efficiently produced.
  • temperature of the hydrosilane-containing fluid at an inlet of the catalyst layer refers to the temperature of the fluid at the boundary where the catalyst layer appears, and for example, in the same way as a thermocouple 107 in FIG. 1 , a thermocouple or the like may be placed at a position where the temperature of the fluid is approximately the same as that at the boundary of the catalyst layer to use the temperature observed thereby as the temperature of the fluid at the inlet of the catalyst layer.
  • temperature of the oligosilane-containing fluid at an outlet of the catalyst layer for example, in the same way as a thermocouple 108 in FIG.
  • thermocouple or the like may be placed at a position where the temperature of the fluid is approximately the same as that at the boundary of the catalyst layer to use the temperature observed thereby as the temperature of the fluid at the outlet of the catalyst layer. Since a fluid and a thermocouple are usually in thermal equilibrium, temperatures measured by the thermocouples may be considered to be the temperatures of the fluids. The temperature may of course be measured by other methods.
  • the specific species of the hydrosilane is not particularly limited as long as it is a compound having at least one silicon-hydrogen (Si—H) bond, and examples of a substituent (atom) other than the hydrogen atom and bonded to the silicon atom include hydrocarbon groups with 1 to 6 carbon atoms (including, for example, saturated hydrocarbon groups, unsaturated hydrocarbon groups, and aromatic hydrocarbon groups).
  • hydrosilane examples include tetrahydrosilane (SiH 4 ), methyltrihydrosilane, ethyltrihydrosilane, phenyltrihydrosilane, and dimethyldihydrosilane.
  • the hydrosilane as a raw material may be selected depending on a desired oligosilane to be produced.
  • a target oligosilane is not particularly limited as long as it is a silane oligomer provided by the coupling of a plurality of (from 2 to 5) individual (mono)silane molecules, and a target oligosilane may have, for example, a branched structure, crosslinked structure, or cyclic structure.
  • the number of silicon atoms of the oligosilane is preferably from 2 to 4, more preferably from 2 to 3, and still more preferably 2 (when monosilane is used as the hydrosilane).
  • oligosilane examples include hexahydrodisilane (Si 2 H), octahydrotrisilane (Si 3 H 8 ), decahydrotetrasilane (Si 4 H 10 ), dimethyltetrahydrodisilane ((CH 3 ) 2 Si 2 H 4 ), and tetramethyldihydrodisilane (CH 3 ) 4 Si 2 H 2 ).
  • the reaction step is a step satisfying all of the conditions (i) to (iii) above.
  • the specific temperatures of the hydrosilane-containing fluid at the inlet of the catalyst layer and the oligosilane-containing fluid at the outlet of the catalyst layer are not particularly limited as long as the temperatures satisfy (i) to (iii) and may be selected as appropriate according to the purpose.
  • the difference between the temperature of the hydrosilane-containing fluid at the inlet of the catalyst layer and the temperature of the oligosilane-containing fluid at the outlet of the catalyst layer is preferably at least 10° C., more preferably at least 30° C., and still more preferably at least 50° C., and is preferably not more than 200° C., more preferably not more than 170° C., and still more preferably not more than 150° C.
  • the temperature of the hydrosilane-containing fluid at the inlet of the catalyst layer is from 200 to 400° C., preferably at least 220° C., and more preferably at least 250° C., and preferably not more than 350° C., and more preferably not more than 300° C.
  • the temperature is at least 200° C., a good reaction conversion is secured, and when the temperature is not more than 400° C., side reactions are suppressed to some extent.
  • the temperature of the oligosilane-containing fluid at the outlet of the catalyst layer is from 50 to 300° C., preferably at least 80° C., and more preferably at least 100° C., and preferably not more than 250° C., and more preferably not more than 200° C.
  • the temperature is at least 50° C., a good reaction conversion is secured, and when the temperature is not more than 300° C., side reactions are suppressed.
  • oligosilane production can be carried out more efficiently.
  • the reaction step it is preferable to heat the hydrosilane-containing fluid with an external heat source and control the catalyst layer with a temperature control [cooling] unit (for example, by circulating a refrigerant through a jacket or the like) so that the outlet temperature of the fluid is lower than the inlet temperature of the fluid in the catalyst layer.
  • a temperature control [cooling] unit for example, by circulating a refrigerant through a jacket or the like
  • a temperature control [cooling] unit for example, by circulating a refrigerant through a jacket or the like
  • the temperature of the fluid can be decreased through the wall of the reactor by the temperature control [cooling] unit installed on the outside of the reactor.
  • a reactor 201 in FIG. 2(A) is structured to be in contact with one temperature control [cooling] unit 206 from the inlet to the outlet as a whole.
  • Temperature control [cooling] units 306 in FIG. 3(A) and temperature control [cooling] units 406 in FIG. 4(A) are a plurality of temperature control [cooling] units divided in the longitudinal direction of the reactor so as to be able to cause a stepwise change in the reactor external temperature.
  • An example of the temperature control [cooling] unit for decreasing the temperature of the fluid flowing through the catalyst layer is an inflow of a refrigerant into a jacketed reaction apparatus.
  • the refrigerant include the following: water vapor; organic refrigerants such as silicone oil, linear paraffin, biphenyl, biphenyl ether, and dibenzyltoluene; and inorganic refrigerants such as a mixture of sodium nitrite, sodium nitrate, and potassium nitrate.
  • cooling may be carried out by air-cooling (the air corresponds to the refrigerant in this case) using, for example, a commercially available tubular furnace.
  • air-cooling the air corresponds to the refrigerant in this case
  • a catalyst layer with a wide tube diameter it is preferable to arrange a cooling tube such as a coil inside so that more efficient temperature control [cooling] can be performed on the catalyst layer.
  • the reactor external temperature is generally at least 20° C., preferably at least 30° C., and more preferably at least 40° C., and is generally not more than 300° C., preferably not more than 280° C., and more preferably not more than 260° C., depending on the fluid temperatures at the inlet and outlet of the catalyst layer.
  • the difference between the temperature of the hydrosilane-containing fluid at the inlet of the catalyst layer and the reactor external temperature is more preferably at least 20° C., and still more preferably at least 50° C.
  • oligosilane production can be carried out more efficiently.
  • FIG. 2(A) to FIG. 4(A) each illustrate a case where the catalyst layer is provided almost all across the reactor to simplify the descriptions
  • the catalyst layer may be provided only at part of the reactor in the manner as shown in FIG. 1 .
  • the temperature control [cooling] unit such as a jacket may be arranged at a position overlapping with at least part of the catalyst layer.
  • the upstream side of a reactor 501 is a preheating zone while a catalyst layer 507 is placed on the downstream side, and an external jacket is sectioned to thereby efficiently increase the temperature to the inlet temperature of the catalyst layer which serves as a reaction zone and decrease the temperature within the reactor where the catalyst layer is arranged.
  • the reaction step is a step including introducing a hydrosilane-containing fluid into a continuous reactor provided with a catalyst layer inside, and the hydrosilane concentration in the introduced fluid, the state of the fluid, a simple substance (such as a carrier gas to be described later) or compound contained in the fluid and other than the hydrosilane, the pressure of the fluid, and the like are not particularly limited and may be selected as appropriate according to the purpose. A detailed description is provided below with specific examples.
  • the hydrosilane concentration in the fluid at the inlet of the catalyst layer is generally at least 20 mol %, preferably at least 30 mol %, and more preferably at least 40 mol % and is preferably not more than 95 mol % and more preferably not more than 90 mol %. If within the indicated ranges, oligosilane production can be carried out more efficiently.
  • the fluid containing hydrosilane as a raw material is preferably a gas and more preferably a gas containing a carrier gas.
  • the carrier gas examples include inert gases such as nitrogen gas and argon gas and hydrogen gas, and it is particularly preferable to contain hydrogen gas.
  • reaction equation (a) While the dehydrogenative coupling of tetrahydrosilane (SiH 4 ) produces disilane (Si 2 H 6 ) as shown in reaction equation (a) below, it is considered that a portion of the produced disilane decomposes, as shown in reaction equation (b) below, into tetrahydrosilane (SiH 4 ) and dihydrosilylene (SiH 2 ). It is also considered that the produced dihydrosilylene undergoes polymerization as shown in reaction equation (c) below to form a solid polysilane (SiH 2 ) n , leading to a decrease in the oligosilane yield, for example.
  • reaction equation (d) When, on the other hand, hydrogen gas is present, it is considered that tetrahydrosilane is produced from dihydrosilylene as shown in reaction equation (d) below, the production of polysilanes is then suppressed, and as a consequence the oligosilane production can be carried out on a long-term and stable basis.
  • the concentration of the hydrogen gas at the inlet of the catalyst layer is preferably at least 1 mol %, more preferably at least 3 mol %, and still more preferably at least 5 mol % and is preferably not more than 40 mol %, more preferably not more than 30 mol %, and still more preferably not more than 20 mol %. If within the indicated ranges, the oligosilane production can be carried out more efficiently.
  • the pressure at the inlet of the catalyst layer within the reactor is preferably at least 0.1 MPa, more preferably at least 0.15 MPa, and still more preferably at least 0.2 MPa and is preferably not more than 10 MPa, more preferably not more than 5 MPa, and still more preferably not more than 3 MPa.
  • the hydrosilane partial pressure is preferably at least 0.0001 MPa, more preferably at least 0.0005 MPa, and still more preferably at least 0.001 MPa and is preferably not more than 10 MPa, more preferably not more than 5 MPa, and still more preferably not more than 1 MPa. If within the indicated ranges, oligosilane production can be carried out more efficiently.
  • the partial pressure of the hydrogen gas with respect to the sum of the partial pressure of hydrosilanes and the partial pressure of oligosilanes is from 0.05 to 5, preferably from 0.1 to 4, and more preferably from 0.02 to 2 (hydrogen gas/(hydrosilanes+oligosilanes)).
  • the hydrosilane-containing fluid When the hydrosilane-containing fluid is caused to flow through using a continuous tubular reactor, the conversion is too low at short contact time with the catalyst (high flow rate) while polysilane production is facilitated if the contact time with the catalyst is too long, and a contact time of from 0.01 seconds to 30 minutes is preferable as a consequence.
  • the reaction step is a step including discharging an oligosilane-containing fluid from the reactor, and examples of a simple substance or compound contained in the fluid and other than the oligosilane include unreacted hydrosilanes and a carrier gas.
  • the reaction step is a step including introducing a hydrosilane-containing fluid into a continuous reactor provided with a catalyst layer inside, and the catalyst is described in detail below with specific examples.
  • a particularly preferable catalyst is a heterogeneous catalyst containing a support and, on the surface and/or in the interior of the support, at least one transition element (hereinafter may be abbreviated as “transition element”) selected from the group consisting of Periodic Table group 3 transition elements, group 4 transition elements, group 5 transition elements, group 6 transition elements, group 7 transition elements, group 8 transition elements, group 9 transition elements, group 10 transition elements, and group 11 transition elements. It is considered that such transition elements promote the dehydrogenative coupling of hydrosilanes, resulting in production of oligosilanes at good efficiencies.
  • transition element-containing catalyst containing, on the surface and/or in the interior of the support, at least one transition element selected from the group consisting of Periodic Table group 3 transition elements, group 4 transition elements, group 5 transition elements, group 6 transition elements, group 7 transition elements, group 8 transition elements, group 9 transition elements, group 10 transition elements, and group 11 transition elements is described in detail below.
  • Examples of the group 3 transition elements in the transition element-containing catalyst include scandium (Sc), yttrium (Y), lanthanoid (La), and samarium (Sm).
  • Examples of the group 4 transition elements include titanium (Ti), zirconium (Zr), and hafnium (Hf).
  • Examples of the group 5 transition elements include vanadium (V), niobium (Nb), and tantalum (Ta).
  • Examples of the group 6 transition elements include chromium (Cr), molybdenum (Mo), and tungsten (W).
  • Examples of the group 7 transition elements include manganese (Mn) and rhenium (Re).
  • Examples of the group 8 transition elements include iron (Fe), ruthenium (Ru), and osmium (Os).
  • Examples of the group 9 transition elements include cobalt (Co), rhodium (Rh), and iridium (Ir).
  • Examples of the group 10 transition elements include nickel (Ni), palladium (Pd), and platinum (Pt).
  • Examples of the group 11 transition elements include copper (Cu), silver (Ag), and gold (Au).
  • transition elements for use in the present invention are the group 4 transition elements, group 5 transition elements, group 6 transition elements, group 8 transition elements, group 9 transition elements, group 10 transition elements, and group 11 transition elements.
  • transition elements are the group 5 transition elements, group 6 transition elements, group 9 transition elements, and group 10 transition elements.
  • transition elements examples include tungsten (W), vanadium (V), molybdenum (Mo), cobalt (Co), nickel (Ni), palladium (Pd), and platinum (Pt).
  • tungsten (W), molybdenum (Mo), cobalt (Co), and platinum (Pt) are particularly preferred for the transition element.
  • the form and composition of the transition element in the transition element-containing catalyst are also not particularly limited, and, for example, the form may be that of a metal (a metal simple substance, an alloy) optionally having an oxidized surface or may be that of a metal oxide (a single metal oxide, a composite metal oxide).
  • the metal and/or metal oxide may be supported at the surface of the support (outer surface and/or within the pores) or the transition element may be introduced into the interior of the support (support framework) by ion exchange or composite formation.
  • Examples of the metal optionally having an oxidized surface include scandium, yttrium, lanthanoid, samarium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold.
  • metal oxide examples include scandium oxide, yttrium oxide, lanthanoid oxide, samarium oxide, titanium oxide, zirconium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, technetium oxide, rhenium oxide, iron oxide, ruthenium oxide, osmium oxide, cobalt oxide, rhodium oxide, iridium oxide, nickel oxide, palladium oxide, platinum oxide, copper oxide, silver oxide, gold oxide and their composite oxides.
  • Examples of the methods of loading the support with the transition element include impregnation and ion-exchange, which use a precursor in solution form, and a method in which a precursor is volatilized by, for example, sublimation, and vapor deposited on the support.
  • Impregnation method is a method in which the support is brought into contact with a solution in which a transition element-containing compound is dissolved and the transition element-containing compound is thereby adsorbed to the surface of the support. Pure water is ordinarily used for the solvent, but organic solvents such as methanol, ethanol, acetic acid, and dimethylformamide, may also be used as long as they dissolve the transition element compound.
  • Ion-exchange method is a method in which a support having acid sites, e.g., zeolite, is brought into contact with a solution in which an ion of the transition element is dissolved, thereby introducing the transition element ion at the acid sites on the support.
  • Pure water is again ordinarily used as the solvent in this case, but organic solvents such as methanol, ethanol, acetic acid, and dimethylformamide, may also be used as long as they dissolve the transition element.
  • Vapor deposition method is a method in which the transition element itself or the transition element oxide is heated in order to volatilize same by, e.g., sublimation, and thereby bring about its vapor deposition on the support.
  • preparation of the metal or metal oxide form desired for the catalyst can be carried out by the execution of treatments such as drying, and calcination in a reducing atmosphere or an oxidizing atmosphere.
  • Examples of the precursor for the transition element-containing catalyst include, in the case of molybdenum, ammonium heptamolybdate, silicomolybdic acid, phosphomolybdic acid, molybdenum chloride, and molybdenum oxide.
  • the examples include ammonium paratungstate, phosphotungstic acid, silicotungstic acid, and tungsten chloride.
  • titanium the examples include titanium oxysulfate, titanium chloride, and tetraethoxytitanium.
  • vanadium the examples include vanadium oxysulfate and vanadium chloride.
  • cobalt the examples include cobalt nitrate and cobalt chloride.
  • the examples include nickel nitrate and nickel chloride.
  • the examples include palladium nitrate and palladium chloride.
  • the examples include a nitric acid solution of diammine dinitro platinum (II) and tetraammine platinum (II) chloride.
  • the specific species of the support of the transition element-containing catalyst is not particularly limited, examples thereof include silica, alumina, titania, zirconia, silica-alumina, zeolites, active carbon, and aluminum phosphate, and the support is preferably any one of silica, alumina, titania, zirconia, zeolites, and active carbon.
  • zeolites are preferred, a zeolite having pores with a minor diameter of at least 0.41 nm and a major diameter of not more than 0.74 nm is preferred, and a zeolite having pores with a minor diameter of at least 0.43 nm and a major diameter of not more than 0.69 nm is particularly preferred.
  • the pore space in the zeolite is considered to act as a reaction field for dehydrogenative coupling, and a pore size of “a minor diameter of at least 0.41 nm and a major diameter of not more than 0.74 nm” is considered to be optimal for suppressing excessive polymerization and bringing about an improved selectivity for an oligosilane.
  • a zeolite having pores with a minor diameter of at least 0.41 nm and a major diameter of not more than 0.74 nm does not mean only zeolites that actually have “pores with a minor diameter of at least 0.41 nm and a major diameter of not more than 0.74 nm”, but also includes zeolites for which the pore “minor diameter” and “major diameter” as theoretically calculated from the crystalline structure respectively satisfy the aforementioned conditions.
  • pore “minor diameter” and “major diameter” reference can be made to “ATLAS OF ZEOLITE FRAMEWORK TYPES, Ch. Baerlocher, L. B. McCusker and D. H. Olson. Sixth Revised Edition 2007, published on behalf of the structure Commission of the International Zeolite Association”.
  • the minor diameter for the zeolite is at least 0.41 nm, preferably at least 0.43 nm, more preferably at least 0.45 nm, and particularly preferably at least 0.47 nm.
  • the major diameter for the zeolite is not more than 0.74 nm, preferably not more than 0.69 nm, more preferably not more than 0.65 nm, and particularly preferably not more than 0.60 nm.
  • the pore diameter of the zeolite is constant because, for example, the cross-sectional structure of the pore is circular, the pore diameter is then regarded as “at least 0.41 nm and not more than 0.74 nm”.
  • the pore diameter of at least one type of pore should be “at least 0.41 nm and not more than 0.74 nm”.
  • the specific zeolite is preferably a zeolite having a framework type code as provided in the database of the International Zeolite Association corresponding to the following: AFR, AFY, ATO, BEA, BOG, BPH, CAN, CON, DFO, EON, EZT, FAU, FER. GON, IMF, ISV, ITH, IWR, IWV, IWW, LTA, LTL, MEI, MEL, MFI, MOR, MWW, OBW, MOZ, MSE, MTT, MTW, NES, OFF, OSI, PON, SFF, SFG, STI, STF, TER, TON, TUN, USI, and VET.
  • AFR AFY, ATO, BEA, BOG, BPH, CAN, CON, DFO, EON, EZT, FAU, FER. GON, IMF, ISV, ITH, IWR, IWV, IWW, LTA, LTL, MEI,
  • Zeolites with framework type codes corresponding to the following are more preferred: ATO, BEA, BOG, CAN, IMF, ITH, IWR, IWW, MEL, MFI, OBW, MSE, MTW, NES, OSI, PON, SFF, SFG, STF, STI, TER, TON, TUN, and VET.
  • Zeolites with framework type codes corresponding to BEA, MFI, and TON are particularly preferred.
  • Examples of zeolites with a framework type code corresponding to BEA include *Beta, [B—Si—O]-*BEA, [Ga—Si—O]-*BEA, [Ti—Si—O]-*BEA, Al-rich beta, CIT-6, Tschernichite, and pure silica beta (the * indicates a mixed crystal of three polytypes with similar structures).
  • Examples of zeolites with a framework type code corresponding to MFI include *ZSM-5, [As—Si—O]-MFI, [Fe—Si—O]-MFI, [Ga—Si—O]-MFI, AMS-1B, AZ-1, Bor-C, Boralite C, Encilite, FZ-1, LZ-105, Monoclinic H-ZSM-5, Mutinaite, NU-4, NU-5, Silicalite, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, ZMQ-TB, and organic-free ZSM-5 (the * indicates a mixed crystal of three polytypes with similar structures).
  • zeolites with a framework type code corresponding to TON include Theta-1, ISI-1, KZ-2, NU-10, and ZSM-22.
  • Zeolites ZSM-5, beta, and ZSM-22 are particularly preferred.
  • the silica-alumina ratio (mol/mol ratio) is preferably from 5 to 10,000, more preferably from 10 to 2,000, and particularly preferably from 20 to 1,000.
  • the overall transition element content in the transition element-containing catalyst is preferably at least 0.01 mass %, more preferably at least 0.1 mass %, and still more preferably at least 0.5 mass % and is preferably not more than 50 mass %, more preferably not more than 20 mass %, and still more preferably not more than 10 mass %. If within the indicated ranges, a good reaction conversion can be secured, and side reactions due to excessive use can be suppressed. As a consequence, oligosilane production can be carried out more efficiently.
  • the transition element-containing catalyst preferably has the form of a molding provided by molding a powder into a spherical shape, cylindrical shape (pellet shape), ring shape, or honeycomb shape.
  • a binder such as alumina and a clay compound, may be used in order to mold the powder. The strength of the molding cannot be maintained when the amount of binder use is too small; when the amount of binder use is too large, this has a negative effect on the catalytic activity.
  • the alumina content (per 100 mass parts of the support (powder) not containing the alumina) is generally at least 2 mass parts, preferably at least 5 mass parts, and more preferably at least 10 mass parts and is generally not more than 50 mass parts, preferably not more than 40 mass parts, and more preferably not more than 30 mass parts. If within the indicated ranges, negative effects on the catalytic activity can be suppressed while the strength of the support is maintained.
  • the transition element-containing catalyst preferably contains at least one main group element (hereinafter may be abbreviated as “main group element”) selected from the group consisting of Periodic Table group 1 main group elements and group 2 main group elements.
  • main group element selected from the group consisting of Periodic Table group 1 main group elements and group 2 main group elements.
  • the form and composition of the main group element in the catalyst is not particularly limited, but examples of the form include the metal oxide (single metal oxide, composite metal oxide) and the ion.
  • the main group element may be supported in the form of the metal oxide or metal salt at the surface of the support (outer surface and/or within the pores) or the main group element may be introduced into the interior (support framework) by ion exchange or composite formation.
  • Examples of the group 1 main group elements include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
  • group 2 main group elements examples include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).
  • sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), calcium (Ca), strontium (Sr), and barium (Ba) is preferred.
  • Impregnation and ion exchange are examples of methods for incorporating the main group element into the transition element-containing catalyst.
  • Impregnation is a method in which the support is brought into contact with a solution in which a main group element-containing compound is dissolved and the main group element is thereby adsorbed to the surface of the support.
  • Pure water is ordinarily used for the solvent, but organic solvents such as methanol, ethanol, acetic acid, and dimethylformamide, can also be used as long as they dissolve the main group element-containing compound.
  • Ion-exchange is a method in which a support having acid sites, e.g., zeolite, is brought into contact with a solution in which an ion of the main group element is dissolved, thereby introducing the main group element ion at the acid sites on the support.
  • Pure water is also ordinarily used as the solvent in this case, but organic solvents such as methanol, ethanol, acetic acid, and dimethylformamide, can also be used as long as they dissolve the main group element ion. Treatments such as drying and firing may be carried out after the execution of impregnation or ion-exchange.
  • examples of the solution include an aqueous lithium nitrate (LiNO %) solution, an aqueous lithium chloride (LiCl) solution, an aqueous lithium sulfate (Li 2 SO 4 ) solution, an acetic acid solution of lithium acetate (LiOCOCH 3 ), and an ethanol solution of lithium acetate.
  • examples of the solution include an aqueous sodium chloride (NaCl) solution, an aqueous sodium sulfate (Na 2 SO 4 ) solution, and an aqueous sodium nitrate (NaNO 3 ).
  • examples of the solution include an aqueous potassium nitrate (KNO 3 ) solution, an aqueous potassium chloride (KCl) solution, an aqueous potassium sulfate (K 2 SO 4 ) solution, an acetic acid solution of potassium acetate (KOCOCH 3 ), and an ethanol solution of potassium acetate.
  • examples of the solution include an aqueous rubidium chloride (RbCl) solution and an aqueous rubidium nitrate (KNO 3 ) solution.
  • examples of the solution include an aqueous cesium chloride (CsCl), an aqueous cesium nitrate (CsNO 3 ) solution, and an aqueous cesium sulfate (Cs 2 SO 4 ) solution.
  • CsCl aqueous cesium chloride
  • CsNO 3 aqueous cesium nitrate
  • Cs 2 SO 4 aqueous cesium sulfate
  • examples of the solution include an aqueous francium chloride (FrCl) solution.
  • examples of the solution include an aqueous calcium chloride (CaCl 2 ) solution and an aqueous calcium nitrate (Ca(NO 3 ) 2 ) solution.
  • examples of the solution include an aqueous strontium nitrate (Sr(NOO 3 ) 2 ) solution.
  • examples of the solution include an aqueous barium chloride (BaCl 2 ) solution, an aqueous barium nitrate (Ba(NO 3 ) 2 ) solution, and an acetic acid solution of barium acetate (Ba(OCOCH 3 ) 2 ) solution.
  • the overall content of the main group element in the transition element-containing catalyst is preferably at least 0.01 mass %, more preferably at least 0.05 mass %, still more preferably at least 0.1 mass %, particularly preferably at least 0.5 mass %, more particularly preferably at least 1.0 mass %, and most preferably at least 2.1 mass % and is preferably not more than 10 mass %, more preferably not more than 5 mass %, and still more preferably not more than 4 mass %. If within the indicated ranges, oligosilane production can be carried out more efficiently.
  • the transition element-containing catalyst may contain a Periodic Table group 13 main group element.
  • a Periodic Table group 13 main group element there are no particular limitations on the form and composition of the Periodic Table group 13 main group element in the catalyst, and, for example, the form may be that of a metal (a metal simple substance, an alloy) optionally having an oxidized surface or may be that of a metal oxide (a single metal oxide, a composite metal oxide).
  • the metal oxide may be supported at the surface of the support (outer surface and/or within the pores) or the Periodic Table group 13 main group element may be introduced into the interior (support framework) by ion exchange or composite formation.
  • Periodic Table group 13 main group element can also restrain the initial hydrosilane (monosilane) conversion and inhibit excessive consumption, and in combination with this can raise the initial disilane selectivity.
  • the catalyst life can also be extended by restraining the initial hydrosilane conversion.
  • Examples of the group 13 main group element include aluminum (Al), gallium (Ga), indium (In), and thallium (TI).
  • the method for incorporating the Periodic Table group 13 main group element into the transition element-containing catalyst is the same as that in the case of Periodic Table group 1 main group elements.
  • the content, the overall content, of the Periodic Table group 13 main group element in the transition element-containing catalyst is preferably at least 0.01 mass %, more preferably at least 0.05 mass %, still more preferably at least 0.1 mass %, particularly preferably at least 0.5 mass %, more particularly preferably at least 1.0 mass %, and most preferably at least 2.1 mass % and is preferably not more than 10 mass %, more preferably not more than 5 mass %, and still more preferably not more than 4 mass %. If within the indicated ranges, oligosilane production can be carried out more efficiently.
  • the present invention is described in additional detail using the Examples and Comparative Examples provided below, but modifications can be made as appropriate insofar as there is no departure from the essential features of the present invention. Accordingly, the scope of the present invention should not be construed as being limited to or by the specific examples given below.
  • the Examples and Comparative Examples were carried out by immobilizing a zeolite in a fixed bed within a reaction tube of a reaction apparatus shown in FIG. 6 (schematic diagram) and flowing through a reaction gas containing tetrahydrosilane that had been diluted with helium gas or the like.
  • the produced gas was analyzed using a GC-17A gas chromatograph from Shimadzu Corporation with a TCD (thermal conductivity detector). A yield of 0% was reported when detection by GC did not occur (below the detection limit).
  • Qualitative analysis of the disilane and so forth was performed by a MASS (mass analyzer).
  • the pores in the zeolites used were as follows.
  • a 1 ⁇ 2 inch stainless steel tube (nominal diameter: 12.7 mm, wall thickness: 1 mm, length: 500 mm) was manufactured and used as a reaction tube 9 , and the reaction zone in FIG. 6 was filled with a catalyst (fill hight: approximately 10 cm).
  • a commercially available tubular furnace (tubular furnace ARF-16KC from Heat Tech Co., Ltd., length: 14 cm) was placed in each of an upper portion (preheating zone) of the reaction tube not filled with the catalyst and a lower portion (reaction zone) of the reaction tube filled with the catalyst, and heating and cooling were performed at the temperatures given in the Examples and Comparative Examples.
  • Thermocouples were inserted from the top and the bottom of the reaction tube to measure fluid temperatures at the inlet and outlet of the catalyst layer.
  • a filter 10 in FIG. 6 was one generally used for sampling of a reaction gas, no sampling operation such as sampling by cooling was included in the Examples, and the reaction gas was directly introduced into the gas chromatograph for analysis. Since the reaction apparatus used in these evaluations was for testing and research, an abatement apparatus 13 was installed in order to discharge the products out of the system in a safe manner.
  • an argon/tetrahydrosilane (monosilane) mixed gas Ar: 20%, SiH 4 : 80% (molar ratio)
  • hydrogen gas at 2 mL/minute
  • helium gas at 1 mL/minute
  • the argon/tetrahydrosilane (monosilane) mixed gas was brought to 4 mL/minute
  • the hydrogen gas was brought to 1 mL/minute
  • the helium gas was stopped.
  • Table 1 shows preset temperatures of the tubular furnaces and temperatures measured by the thermocouple (1) placed in the vicinity of the inlet of the reaction tube (reaction zone) and the thermocouple (2) placed in the vicinity of the outlet of the reaction tube (reaction zone) after each time period had elapsed from the stop of the helium gas.
  • the composition of the reaction gas was analyzed by the gas chromatograph, and the tetrahydrosilane (monosilane) conversion, the hexahydrodisilane (disilane) yield, the selectivity for hexahydrodisilane (disilane), and the space-time yield (STY) of hexahydrodisilane (disilane) were calculated. The results are altogether given in Table 1.
  • the “contact (residence) time” is the residence time within the reactor of the gas flowing through the reactor, i.e., it is the contact time between the hydrosilane and the catalyst.
  • the space-time yield (STY) for hexahydrodisilane (disilane) was calculated using the following formula.
  • Example 2 A reaction was carried out as in Example 1, except that the preset temperatures of the tubular furnaces were changed as shown in Table 2. The results are given in Table 2.
  • the results of Example 2 and Comparative Example 2 are given in Tables 3 and 4, respectively.
  • Example 3 and Comparative Example 3 were respectively carried out as in Example 1 and Comparative Example 1, except that the catalyst was changed to 10 cm 3 of the 1 mass % Pt-loaded ZSM-5 (pellets) prepared in Preparative Example 3.
  • the results of Example 3 and Comparative Example 3 are given in Tables 5 and 6, respectively.
  • Example 4 and Comparative Example 4 were respectively carried out as in Example 1 and Comparative Example 1, except that the catalyst was changed to 10 cm 3 of the 1 mass % Co-loaded ZSM-5 (pellets) prepared in Preparative Example 4.
  • the results of Example 4 and Comparative Example 4 are given in Tables 7 and 8, respectively.
  • Example 5 and Comparative Example 5 were respectively carried out as in Example 1 and Comparative Example 1, except that the catalyst was changed to 10 cm 3 of the 1 mass % Mo Beta (pellets) prepared in Preparative Example 5.
  • the results of Example 5 and Comparative Example 5 are given in Tables 9 (Example 5) and 10 (Comparative Example 5), respectively.
  • Comparative Example 6 was carried out as in Comparative Example 5, except that the temperature of the tubular furnace in the upper portion of the reaction tube was changed to 200° C., and that the temperature of the reaction furnace in the lower portion of the reaction tube was changed to 400° C. The results are given in Table 11 (Comparative Example 6).
  • Comparative Examples 1 to 5 Although initial activity was high as compared with Examples 1 to 5, catalyst deactivation was fast, which demonstrates that reaction results failed rapidly.
  • Comparative Example 6 activity was low from the initial stage, and the production efficiency was lower than that in Examples 1 to 5 and Comparative Examples 1 to 5.
  • Oligosilanes produced by the production method of the present invention are expected to be used as a gas for the production of silicon for semiconductors.

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